Monoazo compounds containing a 4-hydroxyquinolone-2 group



Patented Nov. 14, 1950 I UNITED STATES PATENT OFFICE MONOAZO COMPOUNDSCONTAINING A 4-HYDR-OXYQUINOLONE -2 GROUP Joseph B. Dickey, Rochester,N; Y., 'assign or to Eastman Kodak Company, Rochester, N. Y., acorporation of New Jersey No'Drawing. Serial No.

4 Claims. (01.

This invention relates to new monoazo compounds containin a, 4--hydroxyquinolone -2 group which are valuable in the art of dyeing-orcoloring. Textile materials made of or containing a cellulose alkylcarboxylic acid ester-having 1 two to four carbon atoms in theacid-groups thereof are colored fast'yellow -shades by the new compoundsusingconvenientcoloring meth ods well-known in the art.

The cellulose alkyl c'arboxylic' acid-esters which Gi i k) wherein Arepresents the residue oian aromatic M nucleus are not new. A number ofazo compounds having this general formula have been 7 prepared andtested. Whilethe fastnessto light35 and gas of the dyeings obtained withsomer of y these compounds on cellulose acetate textile materials isgood, it has been found that when wet or damp cellulose acetate materialcolored with one of these dyes ishot-pressed or steamed, the dye issublimed or marked ofi the fabric. This fault definitely limits the usein the textile industry of dyes of this type.

Accordingly, it is an object of my invention to provide new azo dyecompounds containing a 4- hydroxyquinolone-2 nucleus. It is a furtherobject of my invention to provide new yellow dyes for the coloration ofthe aforesaid cellulose alkyl carboxylic acid ester textile materialswhich are of good fastness to light, gas, and washing, and are free fromthe fault of subliming or marking off when steamed or hot-pressed.Another object is to provide a satisfactory process for preparing mynew'compounds.

The new compounds'by means of which the Application January 7, 1948,

foregoing objects are accomplished or made possible have the formula:

wherein R represents the residue of a monocyclic, non-sulionatedaromatic nucleus of the benzene series, R1 represents a hydroxyalkylgroup having two to three, inclusive, carbon lo' 'atoms, an alkoxyalkylgroup havin three tofour, inclusive. carbon atoms, the,B-carboxamidoethylgro'up, the p carbomethoxyethyl group, or the,B-car'boetho'xyethyl group, and X stands for a hydrogen atom, achlorine atom, a bromine o'z'atom, a methyl group, a methoxy group, aetrifiuoromethyl group, or a nitro group.

The azo dye compounds of my invention are I prepared by diazotizing adiazotizable monocyclic, non-sulfonated, aromatic amine of the benzeneseries and coupling the diazonium compound formed with .a4-hydroxyquinolone-2 compound having the formula:

l. wherein R1 and X have the meanings previously assigned to them. Thecouplin reaction is carried out in aqueous alkaline solution followingwhich the reaction mixture is neutralized and the dye compound isrecovered by filtration washedwith water, and dried.

Thre lfollowing examples illustrate the azo dye.

a 500 ,cc.flask' fitted with an agitator andathermometer. 7.6 grams ofdry sodium nitrite are added slowly with vigorous stirring to thesulfuric acid over a period of about one minute during which thetemperature of the mixing rises to -75 0. After cooling the resultingmixture.

to 12-14? C., cc. of cold acetic acid are added, with stirring, whilemaintaining a temperature below 20 C. 16.3 grams ofo-nitro-p-cyanoaniline are then added with continuous stirring andcooling. A clear yellow solution results, and diazotization is completewhen a drop of solution dissolves completely in a small beaker of water.

20.5 grams of N-fl-hydroxyethyl-4-hydroxyquinolone-2 are dissolved in200 cc. of Water containing 30 grams of sodium carbonate, and theresulting solution is cooled to l0 C. The diazo solution prepared asdescribed above is slowly added with stirring and concurrently with itsaddition an aqueous solution of sodium hydroxide is added in suflicientamount to maintain the reaction mixture slightly alkaline. A temperatureof 0-10 C. is maintained throughout the reaction which takes place. Uponcompletion of the coupling reaction the mixture is made acid to litmusby the addition of hydrochloric acid, and the dye compound formed isrecovered by filtration, washed free of salts with water, and dried. Thedye compound has the formula:

mom-0H and colors cellulose acetate yellow shades.

Example 2 13.8 grams of m-nitroaniline are dissolved in 150 cc. of waterto which has been added 25 cc. of 36% hydrochloric acid and theresulting solution is cooled to 0-10 C. by the addition of ice. Them-nitroaniline is diazotized by adding with stirring, 6.9 grams ofsodium nitrite dissolved in water while maintaining a temperature of 010C.

20.5 grams of N-fi-hydroxyethyll-hydroxyquinolone-Z are dissolved in 200cc. of a solution of 30 grams of sodium carbonate. After cooling theresulting solution to 0-10 0., the diazonium solution prepared asdescribed above is slowly added with stirring and further cooling. Uponcompletion of the coupling reaction which takes place, the mixture isrendered neutral to litmus by the addition of hydrochloric acid. Theprecipitated dye product is collected on a suction filter, washed withwater, and dried. The dye compound obtained has the formula;

and colors cellulose acetate yellow shades.

By the use of 13.8 grams of p-nitroaniline in place of m-nitroaniline inthe example just given, a dye compound is obtained which also colorscellulose acetate yellow shades.

Eaiample 3 ams of sodium carbonate.

' dried. The azo dye compound diazonium solution prepared as describedabove is slowly added with stirring while maintaining a temperature of0-10 C. Upon completion of the coupling reaction which occurs, themixture is made neutral to litmus by adding hydrochloric acid. Theprecipitated dye product is recovered by filtration, washed with water,and dried. The dye compound thus obtained has the formula:

HzCHr-OH and colors cellulose acetate yellow shades.

Example 4 to litmus by adding hydrochloric acid and the precipitatedproduct is recovered by filtration washed with water, and dried. The azodye compound thus obtained has the formula:

IEhCHzCONH: and colors cellulose acetate yellow shades.

Example 5 20.6 grams of 2-trifiuoromethyl-5-nitroaniline are diazotizedby adding 6.9 grams of sodium nitrite dissolved in water to an icedsolution of the compound in cc. of water containing 25 cc. of 36%hydrochloric acid.

The resulting solution of diazonium compound is slowly added withstirring to an iced solution of 20.5 grams ofN-B-hydroxyethyl-4-hydroxyquinolone-Z in 200 cc. of water containing 30Upon completion of the coupling reaction which occurs, the mixture ismade neutral to litmus by adding hydrochloric acid, and the precipitatedproduct is re-' covered by filtration, washed with water, and obtainedhas the formula:

IHzCHzP-OH and colors cellulose acetate yellow shades.

Example 6 13.8 grams of m-nitroaniline are diazotized in accordance withthe diazotization procedure described in Example 2 and the resultingsolution of diazonium compound is slowly added with stirring to an icedsoluton of 21.9 grams of N-p-hydroxypropyl-4-hydroxyquinolone-2 in 200cc. of water containing 30 grams of sodium carbonate. Upon completion ofthe coupling reaction which occurs, themixture is neutralized withvhydroe chloric acid, and the precipitateddye compound is recovered byfiltration, washed with water, and dried. The dye compound obtained hasthe formula:

dmonom and colors cellulose acetate yellow shades.

Example 7 18.6 grams of Z-aminobenzene methylsulfonamide are dissolvedin 150 cc. of water containing :25 cc. of 36% hydrochloric acid anddiazotized by adding with stirring an aqueous solution of 6.9 grams ofsodium nitrite while maintaining a temperature of 0-10" C.

26.5 grams of N -e,' -dihydroxypropyl 4 hydroxy-8-methoxyquinolone-2 aredissolved in 200 2 and colors cellulose acetate yellow shades.

' Example 8 A. 18.3 grams of 3,5-dinitroaniline are dissolved in 225 cc.of hot glacial acetic acid and the resulting solution is then cooledrapidly to room temperature.

B. 7.6 grams of sodium nitrite are dissolved in 55 grams of 100%sulfuric acid at C. and the resulting solution is warmed to 70 C.following which it is cooled to 15-20" C.

The mixture prepared in B is added to the mixture prepared in A over aperiod of 30 to 45 minutes while stirring and maintaining a temperatureof l520 C. Stirring is continued at room temperature for several hoursand then one gram of urea is added to remove any excess nitrous acid.

23.3 grams of N-p-methoxyethyl-4-hydroxy-7- methy1quinolone-2 aredissolved in 200 cc. of water to which has been added 31 grams of sodiumcarbonate and the resulting solution is cooled to a temperature of 1-l0C. by the addition of ice. The diazo solution prepared as describedabove is then added with stirring while con- 6 C. is maintainedthroughout the reaction which occurs. At the conclusion of the couplingreaction, the mixture is made acid to litmus by the addition of aceticacid,'and the dye com-' pound formed is recovered by filtration, washedwith water, and dried. The dye compound tained has the formula:

and colors cellulose acetate yellow shades.

. Example 9 I 23.1 grams of 2-amino-5-nitrobenzenemethylsulfonamide arediazotized by dissolving in 1 cc. of water containing 25 cc. of 36%hydrochloric acid and adding to the resulting solution 6.9 grams ofsodium nitrite dissolved in water while stirring and cooling to maintaina temperature of 040 C.

26.1 grams of N-fi-carboethoxyethyl-4-hydroxyquinolone-2 are added to200 cc. of water containing 30- grams of sodium carbonate. To theresulting mixture is added the solution of 'diazonium compound prepared:as described above while stirring and maintaining a temperature of0-10" C. Upon completion of the coupling reaction which takes place, themixture is made neutral to litmus by the addition of hydrochloric acidand the precipitated dye product is rte-- covered by filtration, washedwith water, and dried. The azo dye compound obtained has the formula:

NOz-N=N O NHCH;

and colors cellulose acetate yellow shades.

Example 10 HqCHzC O OCHnCHa 5-chloroquinolone-2 are dissolved in 200:cc. of

water containing 30 grams of sodium carbonate. While maintaining atemperature of 0-l0 C. in the reaction mixture the solution of diazoniumcompound prepared as described above is slowly added with stirring. Acoupling reaction takes place at the completion of which the mixture ismade neutral to litmus by adding hydrochloric acid. The precipitated dyeproduct is recovered by filtration, washed with watenand dried. The

azo dye compound obtained has theformulaz" N (trimmers-on andcolors'cellulose acetate yellowshacles.-

7 Example 11 action is complete and the reaction mixture is neutralizedwith hydrochloric acid. The precipitate is then collected on a suctionfilter, washed with water, and dried. The azo dye compound obtained hasthe formula:

' SOzCHa O: N/ CF;

and colors cellulose acetate yellow shades.

Example 12 15.2 grams of o-nitro-p-methylaniline are dissolved in 150cc. of water containing 25 cc. of 36% hydrochloric acid. 6.9 grams ofsodium nitrite dissolved in water are then added while stirring andcooling to -10 C. to effect diazotization.

The resulting solution of diazonium compound is added slowly withstirring to an iced solution of 25.5 grams ofN-fi-hydroxypropyl-4-hydroxyfi-chloroquinolone-Z in 200 grams of Watercontaining 30 grams Of sodium carbonate. When the coupling reactionwhich takes place is complete, the reaction mixture is neutralized withhydrochloric acid, and the precipitated dye product is collected on asuction filter, washed with water, and dried. The azo dye compoundobtained has theformula:

16.8 grams of o-nitro-p-methoxyaniline are dissolved in 150 cc. of watercontaining 25 cc. of 36% hydrochloric acid. While stirring and coolingto maintain a temperature of 0-10 0. 6.9 grams of. sodium nitritedissolved in water are added to efiect diazotization.

26,5 grams of N-fi-methoxyethyl-4-hydroxy-6- nitroquinolone-Z are addedto 200 cc. of water containing 30 grams of sodium carbonate and to theresulting mixture is added with stirring and cooling the solution ofdiazonium compound prepared as described above. The temperature of thecoupling reaction which occurs should not. be

allowed to rise above C. When the reaction is complete, the mixture isrendered neutral to litmus by the addition of hydrochloric acid, and

the precipitated dye.:product is. recovered by fil- 8 tration, washedwith water, and dried. The dye compound obtained has the formula: r I

| NOz 0- N HzCHFOCHa and colors cellulose acetate yellow shades.

Example 14 21.6 grams of 2-amino-S-nitrophenylmethyl sulfone aredissolved in cc. of water contain ing 25 cc. of 36% hydrochloric acidand diazotized by adding 6.9 grams of sodium nitrite dissolved in waterwhile stirring and cooling to maintain a temperature of 010 C.

23.2 grams of N-B-carboxamidoethyl-4-hy-J litmus by adding hydrochloricacid and the precipitate formed is recovered by filtration, washed withwater, and dried. The dye compound obtained has the formula:

(111201120 ONE:

and colors cellulose acetate yellow shades.

ExampZe 15 13.8 grams of m-nitroaniline are diazotized as described inExample 2 and the resulting solution of diazon'ium compound is addedwith stirring to an iced solution of 32.7 grams of N-B-carbomethoxyethyl4 hydr'oxy-G-bromoquino1one- 2 in 200 cc. of water containing 30 gramsof sodium carbonate. A coupling reaction occurs with the evolution ofheat which may necessitate further cooling to maintain a reactiontemperature of -0-l0 C. Upon completion of the coupling reaction themixture is made neutral to litmus by adding hydrochloric acid and theprecipitated dye compound is recovered by filtration, washed with Water,and dried. The azo dye compound obtained has the formula:

and colors cellulose acetate yellow shades. I

The foregoing examples are intended merely to illustrate the manner inwhich the azo dyes ineluded within the scope of my invention areprepared. It will be obvious to those skilled in the art that otherspecific dyes can be prepared by diazotizlng any diazotizablemonocyclic, non-sulfonated, aromatic amine of the benzene series andcoupling the resulting diazonium compound with any 4-hydroxyquinolone-2compound having the general formula hereinbefore illustrated byemploying the'procedure for the coupling reacamong-H 17 on CH3SO1QN= fNO: 0 N/ HzCHCHI 18 OH f I Q 'N/ Y HI HZOHPOH 19 OH cH@0o -QN= in o, 0 vN JHQCHPOCHICHI OHa 3--N=N l foz O N dmomoooom I g NO: 0 N/ I dnzonkoom22. S|O2NH2 (RH HaCH2-OH 23. Nos OH HaCHz-OH Several of the4-hydroxyquinolone-2 compounds which I employ as coupling compounds havenot hitherto been described. In order that my invention shall be moreclearly understood several examples of the preparation of thesecompounds are set forth hereinafter.

Several different methods have been applied to the preparation of4-hydroxyquinolone-2 compounds by prior workers in the field. The methodwhich I prefer is based on the process disclosed in German Patent No.287,803. This process comprises heating N-alkyl-anthranilic acid withacetic nhydride to obtain N-alkyl-4- hydroxyquinolone-Z compounds.Compounds of this type wherein the 5, 6, 7, and 8 positions containsubstituents other than a carboxylic acid group or a sulfonic acid group(for example, a chlorine atom) are also prepared according to thisprocess and are disclosed in U. S. Patent No. 1,969,463.

I have found that a compound having the formula:

-OOOH 1 wherein R1 and X have the meanings previously assigned to themwhen heated with acetic anhydride at C. for about 30 minutes yields a4-hydroxyquinolone-2 compound having the formula:

OH X i wherein R1 and X have their previously given meanings.

The manner of preparation which I have just described will be furtherillustrated by the following examples. Easample A Example B 41.8 gramsof N-p-methoXyethyl-4-methylanthranilic acid are dissolved in 60 gramsof acetic anhydride and the resulting solution is heated under refluxwith stirring at about 130 C. for 30 minutes. The reaction mixture ispoured into 300 cc. of 10% sodium hydroxide solution and agitated toeffect complete solution. The reaction product is precipitated by addinghydrochloric acid until the cold reaction mixture is acid to congo redfollowing which it is recovered by filtration, washed with cold water,and dried. The N-B methoxyethyl 4-hydroxy 7-methylquinolone-2 thusobtained in good yield can be coupled with the hereinbefore mentioneddiazo compounds without further purification.

Example 48.2 grams of N-flfY-dihYdI'OXYDIOPYl-3-methoxy-anthranilic acidand 60 grams of acetic anhydride are heated together under reflux, withstirring, at 130 C. for 30 minutes. The reaction product is worked upand recovered in accordance with the procedure described in Example A.The N-fi -dihydroxypropyl-4-hydroxy-8- 'methoxyquinolone-2 thus obtainedin good yield can be coupled with the hereinbefore mentioned diazocompounds without further purification.

1 Example D 60.4 grams of N-fl-carbomethoxyethyl-S-bro- -mo-anthanilicacid are dissolved in 60 grams of acetic anhydride and theresultingsolution is heated under reflux with stirring at 130 C. for

'30 minutes. The reaction product is worked up and recovered accordingto the procedure described in Example A. TheN-p-carbomethoxyethy1-4-hydroxy-6-bromoquinolone-2 thus obtained in goodyield is coupled with the beforeillustrated diazo compounds to producevaluable azo dye compounds of my invention.

Example I.

45.8 grams of N-v-hydroxypropyl-fi-chloroanthranilic acid and 60 gramsof'acetic anhydride are heated together for about 30 minutes at 130 :C.The reaction product formed is then worked up and recovered inaccordance with the procedure described in Example A. The 1 T'y-hydroxypropyl-4-hydroxy-5-chloroquinolone-2 thus obtained in ood yield iscoupled with the hereinbefore illustrated diazo compounds withoutfurther purification.

It will be apparent to oneskilled in the art that any of the4-hydroxyquinolone-2 compounds which I employ as coupling compounds canbe prepared using the procedure illustrated in the foregoing examples.

Several of the N-substituted-anthranilic acid compounds which I employin the preparation of'the coupling compounds just described have nothitherto been disclosed. The preparation of the compounds having theformula:

OOOH

derivatives.

Example F 34.6 grams of sodium 4-methylanthranilate and grams ofB-methoxyethyl chloride are added to '70 cc. of water and the resultingmixture is heated under reflux for two hours. On cooling, the crudeproduct precipitates and is collected on a suction filter. The solidproduct is .1 then dissolved in 100 cc. of 10% sodium hydroxide solutionand reprecipitated by acidifying the alkaline solution with hydrochloricacid. The N-e-methoxyethyl-4-methylanthranilic acid is recovered byfiltration, washed with water, and dried.

Example G 37.8 grams of sodium 3-methoxyanthranilate and 24 grams offi,'ydihydroxypropyl chloride are dissolved in cc. of water and theresulting solution is heated under reflux for about two hours. The crudereaction product which separates on cooling is recovered and redissolvedin 10% sodium hydroxide solution. Hydrochloric acid is added to acidifythe solution and the N-fim-dihydroXypropyl-3-methoxyanthranilic acidwhich precipitates is recovered by filtration, washed with cold water,and dried.

Example H 40.8 grams of sodium 6-chloroanthranilate, 20 grams oftrimethylene chlorohydrin, and cc. of water are heated under reflux fortwo hours. A good yield of N-y-hydroxypropyl-fi-chloroanthranilic acidis recovered from the reaction mixture using the procedure described inExample F.

Example I 31.8 grams of sodium anthranilate, 20 grams ofl-chloro-Z-hydroxypropane and 80 cc. of water are heated together underreflux for two hours following which the reaction product is worked upand recovered in accordance with the procedure described in Example F.N-fi-hydroxypropylanthanilic acid is thus obtained in good yield.

Compounds having the formula:

-GOOH wherein B represents a B-carbomethoxyethyl group, ap-carboethoxyethyl group, or a B-carboxamidoethyl group and X has itspreviously given meaning are prepared'by heating methyl acrylate, ethylacrylate, and acrylamide respectively with anthranilid acid or anX-substituted derivative thereof in the presence of glacial acetic acid.The following examples illustrate the method of preparing thesecompounds.

Example J 27.4 grams of anthranilic acid, 30 grams of ethyl acrylate,and 5 cc. of glacial acetic acid are heated under reflux on a steam bathfor hours. The excess ethyl acrylate is removed by distilling themixture with steam, and the residue is allowed to cool to crystallizethe N-pcarboethoxyethylanthranilic acid which is then collected on asuction filter, washed with water, and dried.

Example K 43.2 grams of 5-bromoanthranilic acid, 30 grams of methylacrylate, and 5 cc. of glacial acetic acid are heated together underreflux on a steam bath for 150 hours. The excess methyl acrylate isremoved by distillation with steam and the aqueous residue is allowed tocool to crystallize the N-p-carbomethoxyethyl-5-bromo anthranilic acidwhich is then recovered by filtration, washed. with water and dried.

Example L 27.4 grams of anthranilic acid, 15 grams of acrylamide, andcc. of glacial acetic acid are heated together under reflux on a steambath for 150 hours. The reaction mixture is then poured into 100 cc. of10% sodium hydroxide and agitated to dissolve the reaction product. Theresulting solution is acidified by adding hydrochloric acid, and theprecipitated N-B-carboxamidoethylanthranilic acid is recovered byfiltration, Washed with water and dried.

The azo dye compounds of my invention are readily applied to thecoloration of textile materials made of or containing cellulose acetate,for example, by employing conventional direct dyeing methods. To form anaqueous dye bath or dispersion the dye in finely divided condition isadvantageously first pasted with a suitable dispersing agent such asTurkey red oil, soap, sulfite cellulose solution, or an oleyl glycerylsulfate and the resulting paste is dispersed in water. The material tobe colored is immersed in the dye bath at a temperature approximating C.following which the temperature is gradually raised to -90 C. andmaintained at this point until dyeing is complete, usually one half hourto two hours. Upon completion of the dyeing operation the textilematerial is removed from the dyebath, Washed with soap, rinsed well withwater, and dried.

I claim:

1. The monoazo dye compounds having the forwherein R represents theresidue of a monocyclic, non-sulfonated, aromatic nucleus of the benzeneseries and X stands for a member se- :3-

lected from the group consisting of a hydrogen atom, a chlorine atom, abromine atom, a methyl group, a methoxy group, a trifluoromethyl group,and a nitro group.

2. The monoazo dye compounds having the forwherein R represents theresidue of a monocyclic, non-sulfonated, aromatic nucleus of the benzeneseries.

3. The azo dye compound having the formula:

O O N 2 N 3112013120 ONHZ JOSEPH B. DICKEY.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,969,463 Holzack et a1. Aug. 7,1934 2,323,315 Dickey et a1 July 6, 1943 2,364,347 Dickey et a1 Dec. 5,1944 2,391,886 Dickey Jan. 1, 1946

3. THE AZO DYE COMPOUND HAVING THE FORMULA: